JP5398541B2 - Epoxy-terminated thickener pre-chain extended with hydroxy ester and process for producing the same - Google Patents

Description

  The present invention relates to the field of toughness improvers.

  Polymers have long been used as materials. However, some polymers have the problem that the polymer matrix breaks under sudden impact stress, ie its toughness is low. In particular, polymer matrices based on epoxy resins are very hard but in many cases are not very impact resistant. Therefore, attempts to improve the impact resistance have been made for a long time.

  This attempt has been made so far, for example, using specific copolymers called so-called liquid rubbers. Such liquid rubbers can be chemically incorporated into the matrix by using chemically reactive groups such as hydroxyl, carboxyl, vinyl, or amino groups. For example, there has been a reactive liquid rubber butadiene / acrylonitrile copolymer that has been terminated with a hydroxyl, carboxyl, vinyl, or amino group for some time, which is sold by BF Goodrich or Noveon under the trade name Hycar®. Have been supplied. The starting material used in these is always a carboxyl-terminated butadiene / acrylonitrile copolymer, to which a large excess of diamine, diepoxide, or glycidyl (meth) acrylate is usually added. However, this has the effect of increasing the viscosity on the one hand, and on the other hand a very large amount of unconverted diamine, diepoxide, or glycidyl (meth) acrylate, which must be removed in a complex manner. Or otherwise has a significant adverse effect on the mechanical properties).

  However, in many cases what is desired is to obtain further enhanced impact resistance and to have a wider variety of toughening agents. One such possibility in this direction is to chain extend the epoxy-terminated polymer with bisphenols or to use a high molecular weight epoxy resin in toughness modifier preparation. Again, depending on the reaction form, a large amount of unconverted bisphenol or a large amount of chain-extended epoxy resin is produced, both of which can immediately adversely affect the properties of the composition. Furthermore, such adducts rapidly become no longer liquid, and as a result, compositions containing such toughness improvers are often no longer applicable in a reliable manner. Furthermore, the use of bisphenols results in reduced storage stability.

  Accordingly, an object of the present invention is to provide a toughness improving agent having a terminal functional group, which can solve the problems of the prior art. The polymers as claimed in claims 1, 11, 13, and 14 provide such polymers. All of these can be prepared from the carboxyl-terminated polymers described in claim 11 which can be obtained from readily available carboxyl-terminated butadiene / acrylonitrile copolymers. The possibility arising from different molecules for pre-chain extension and end termination allows a wide variety of different toughening agents and makes it possible to meet the requirements. These polymers terminated with functional groups have the great advantage that they have a narrow molecular weight distribution and a very high proportion of molecules suitable as toughness improvers.

  This advantage is achieved through the process for preparing a carboxyl-terminated polymer according to claim 11, which serves as a starting point for the preparation of the polymer according to claims 1, 13, and 14, in particular with end-capping at the end groups according to claim 17. Born through a process comprising two steps for preparing the prepared polymer. The method as claimed in claim 15 ensures that all unconverted reactants present are only those substances which already act as toughness improvers, which substances are further claimed in claim 1, 13 or 14. It reacts in any reaction step that leads further to the described polymer to give a reactive toughness modifier. Thus, very little (if any) of the compound that adversely affects the mechanical properties is formed, which can provide a very effective toughening agent. Despite the many possibilities arising from prechain extension and epoxy termination, this polymer has a surprisingly low viscosity.

  As described in claim 18, the polymers described in claims 1, 11, 13, and 14 can be widely used as a means for increasing the impact resistance of a polymer matrix. Particularly preferred is their use in an epoxy resin matrix.

  Further aspects of the invention relate to a composition comprising a polymer according to claim 1, 11, 13, or 14 and a cured composition according to claims 24 and 25.

  Particularly preferred is the use of such polymers in adhesives, particularly thermosetting epoxy resin adhesives. They have very good impact resistance.

  Preferred embodiments of the invention are the subject matter of the dependent claims.

In a first aspect, the present invention relates to an epoxy-terminated polymer of formula (I)

In the above formula, R ¹ is a divalent group after the terminal carboxyl group is removed from the carboxyl-terminated butadiene / acrylonitrile copolymer CTBN. Further, R ² is a residue after removing n epoxy groups from the polyepoxide PEP, and R ^{2 ′} is H or a group linked to R ² . Further, Y ¹ and Y ² are each independently H or methyl. R ³ is a residue after removing two glycidyl ether groups from diglycidyl ether DGE. Finally, n is 2-4, preferably 2.

More particularly, R ¹ is a group obtained by formal removal of the carboxyl group of the carboxyl-terminated butadiene / acrylonitrile copolymer CTBN marketed by the company Noveon under the name Hycar® CTBN. This preferably has the structure of the following formula (IV).

In this formula, the broken line represents the binding site of two carboxyl groups. R is a linear or branched alkylene group having 1 to 6 carbon atoms, in particular 4 carbon atoms, which may optionally be substituted with an unsaturated group. In an embodiment to be mentioned in particular, the substituent R is a substituent of the formula (VII), in which the broken line again represents the binding site.

  Furthermore, the index q is 40-100, in particular 50-90. Furthermore, the labels b and c represent structural elements derived from butadiene, and a represents a structural element derived from acrylonitrile. The indices x, m, and p then represent values that describe the proportions of the structural elements a, b, and c relative to each other. The index x represents 0.05 to 0.3, the index m represents 0.5 to 0.8, the index p represents 0.1 to 0.2, provided that the sum of x, m, and p is Conditionally equal to 1.

  It should be understood by those skilled in the art that the structure of formula (IV) and the additional structures shown in formulas (V ′ ″) and (VI ′ ″) are also simplified expressions. Is clear. The units a, b and c, or d and e, or d 'and e' can thus be arranged with each other, randomly, alternately or as blocks. Thus, more particularly, formula (IV) is not necessarily a triblock copolymer.

の構造要素を意味すると理解される。特に好ましいエポキシ基は、グリシジルエーテル基：

である。後者の式中のＹ^１がHである場合だけでなく、本明細書では、簡単のために、「グリシジルエーテル基」は、式中のＹ^１がメチルである基をも意味する。 The R ² group is a residue after removing n epoxy groups from the polyepoxide PEP. The epoxy group is an epoxylane ring:

Is understood to mean the structural element of Particularly preferred epoxy groups are glycidyl ether groups:

It is. Not only when Y ¹ in the latter formula is H, but for the sake of simplicity herein, “glycidyl ether group” also means a group wherein Y ^{1 in} the formula is methyl.

  The polyepoxide can be produced by known methods, for example by oxidation of the corresponding olefin or by reaction of epichlorohydrin with the corresponding polyol.

  The polypeptide PEP is a diepoxide, a triepoxide or a tetraepoxide, in particular a diglycidyl ether, a triglycidyl ether or a tetraglycidyl ether. Such polyepoxides or polyglycidyl ethers are known in the art as epoxy reactive diluents or as epoxy resins.

In one embodiment, the polyepoxide PEP is an aliphatic or cycloaliphatic polyglycidyl ether, preferably an aliphatic or cycloaliphatic diglycidyl ether. For example,
- saturated or unsaturated, branched or unbranched, cyclic or open-chain divalent C ₂ -C ₁₀ alcohol glycidyl ethers, (e.g., ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol di Glycidyl ether, octanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether).
-Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open chain tri- or tetrafunctional alcohols (eg epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythritol, etc.) Or polyglycidyl ethers of aliphatic polyols (eg glycerol, trimethylolpropane, etc.).
-Epoxidized dicarboxylic acids such as diglycidyl phthalate, diglycidyl tetra- and hexahydrophthalate, and diglycidyl esters of fatty acid dimers.

More particularly, the aliphatic or cycloaliphatic diglycidyl ether is a diglycidyl ether of the following formula (V ″) or (V ″ ′).

  In these formulas, r ′ is 1 to 9, in particular 3 or 5. Furthermore, q ′ is 0 to 10 and t ′ is 0 to 10, provided that the sum of q ′ and t ′ is 1 or more. Finally, d ′ is a structural element derived from ethylene oxide, and e ′ is a structural element derived from propylene oxide. Thus, the formula (V ′ ″) is (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (poly) ethylene glycol / propylene glycol diglycidyl ether, where the unit d ′ And e ′ may be arranged in blocks, alternating or randomly.

  Particularly suitable aliphatic or cycloaliphatic diglycidyl ethers are ethylene glycol diglycidyl ether, butanediol diglycidyl ether, or hexanediol diglycidyl ether.

  In a further aspect, the polyepoxide PEP is a polyepoxide prepared by olefin oxidation.

  A preferred example of such a polyepoxide PEP is a polyepoxide having at least one epoxy group, which is prepared by oxidation of a cyclohexenyl group or a cyclohexenylene group.

およびポリカルボン酸のポリエステル、3,4-エポキシシクロヘキシルメチルアルコール、特にビス(3,4-エポキシシクロヘキシルメチル)アジペートである。これらの式中、ｖは２〜８であり、Ｒ^６およびＲ^６’は、それぞれ独立に、Ｈ、またはＣ_１〜Ｃ_６アルキル基である。指数ｕおよびｕ’は、それぞれ０〜５であり、特に１〜５であり、但しｕ＋ｕ’≧１、特にｕ＋ｕ’≧２であることを条件とする。特に好適な例は、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート、ビス(3,4-エポキシシクロヘキシルメチル) アジペート、1,2,7,8-ジエポキシオクタン、1,2,3,4-ジエポキシブタン、および1,2,5,6-ジエポキシシクロオクタンである。 A preferred polyepoxide PEP of this type is

And polyesters of polycarboxylic acids, 3,4-epoxycyclohexylmethyl alcohol, in particular bis (3,4-epoxycyclohexylmethyl) adipate. In these formulas, v is 2 to 8, and R ⁶ and R ^{6 ′} are each independently H or a C _{1 to} C ₆ alkyl group. The indices u and u ′ are each 0-5, in particular 1-5, provided that u + u ′ ≧ 1, in particular u + u ′ ≧ 2. Particularly suitable examples are 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1,2,7,8-diepoxyoctane, 1,2, 3,4-diepoxybutane and 1,2,5,6-diepoxycyclooctane.

In a further embodiment, the polyepoxide PEP is an aromatic diglycidyl ether. These are firstly so-called epoxidized novolaks, and secondly have R ² groups of the following formula (V ′) after removal of the two glycidyl ether groups from the aromatic diglycidyl ether.

  In the above formula, R ″ ″ is independently H, methyl, or ethyl, and z ′ is 0 or 1, and therefore o-phenylene, m-phenylene, p-phenylene, and methyl from them. It is a structure derived by substitution of a group or an ethyl group into a ring.

  In a further aspect, the polyepoxide PEP is an epoxy resin. The epoxy resin may be a liquid epoxy resin or a solid epoxy resin.

  The term “solid epoxy resin” is well known to those skilled in the epoxy art and is used in contrast to “liquid epoxy resin”. The glass transition temperature of the solid resin is higher than room temperature, i.e., they can be finely pulverized into a powder that flows freely at room temperature.

A preferred solid epoxy resin has the following formula (VIII):

In the above formula, the substituents R ⁴ , R ⁵ , and Y ² are each independently H or CH ₃ . Furthermore, the index S1 is greater than 1.5, in particular 2-12.

  As used herein, the use of the term “independently” in connection with a substituent, residue, or group is a definition in which substituents, residues, or groups indicated by the same symbol are simultaneously different within the same molecule. Should be interpreted as appearing in

  Such solid epoxy resins are commercially available from, for example, Dow, Huntsman, or Hexion.

  Compounds of formula (VIII) having an index S1 of 1 to 1.5 are referred to by those skilled in the art as semisolid epoxy resins. For the present invention, they are considered to be solid resins as well. However, a preferred solid epoxy resin is a solid epoxy resin in a narrow sense, that is, the index S1 has a value larger than 1.5.

A preferred liquid epoxy resin has the following formula (IX).

In this formula, the substituents R ⁴ , R ⁵ , and Y ² are each independently H or CH ₃ . Furthermore, the index S1 has a value of 0-1. It is preferred that S1 has a value less than 0.2.

  Accordingly, they are preferably diglycidyl ethers of bisphenol A (DGEBA), diglycidyl ethers of bisphenol F, and diglycidyl ethers of bisphenol A / F (the symbol “A / F” is used herein for the reactants) Represents a mixture of acetone and formaldehyde used as Such liquid resins include, for example, Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman), or DER® 331 or DER®. Available as 330 (Dow) or Epikote 828 (Hexion).

In a particularly preferred form, the R ² group represents the following formula (V) or (V ′):

  In these formulas, R ′, R ″, and R ′ ″ are each independently H, methyl, or ethyl, z is 0 or 1, and s is 0 or 0.1-12. .

  A particularly preferred polyepoxide PEP is bisphenol A diglycidyl ether.

The R ³ group is a group after removing two glycidyl ether groups from diglycidyl ether DGE. The diglycidyl ether DGE option basically corresponds to the polyepoxide PEP option already described in detail as diglycidyl ether.

More particularly, the diglycidyl ether DGE is an aliphatic or cycloaliphatic diglycidyl ether, in particular a diglycidyl ether of the following formula (VI ″) or (VI ″ ″).

  In these formulas, r is 1 to 9, in particular 3 or 5. Furthermore, q is 0-10, t is 0-10, provided that the sum of q and t is 1 or more. Finally, d is a structural element derived from ethylene oxide, and e is a structural element derived from propylene oxide. Thus, the formula (V ′ ″) is (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (poly) ethylene glycol / propylene glycol diglycidyl ether, where the units d and e may be arranged in blocks, alternating or randomly.

  Particularly suitable aliphatic or cycloaliphatic diglycidyl ethers are ethylene glycol diglycidyl ether, butanediol diglycidyl ether, or hexanediol diglycidyl ether.

In a further particularly preferred embodiment, the diglycidyl ether DGE is a diglycidyl ether having the following formula (VI) or (VI ′) corresponding to the R ³ group after removal of the two diglycidyl ether groups.

  In these formulas, R ′, R ″, and R ′ ″ are each independently H, methyl, or ethyl, z is 0 or 1, and s is 0 or 0.1-12. .

  A particularly preferred diglycidyl ether DGE is bisphenol F diglycidyl ether.

The epoxy-terminated polymer of formula (I) can be prepared as follows:
In the first step ("preliminary chain extension"), a carboxyl-terminated butadiene / acrylonitrile copolymer CTBN of the formula HOOC-R ¹ -COOH and polyepoxide PEP are combined in a stoichiometric ratio (n ′ ≧ n) HOOC-R. A carboxyl-terminated polymer of the following formula (II) is prepared using ^1- COOH.

が２以上となる量で用いる。 For this reaction, the polyepoxide PEP and HOOC-R ¹ -COOH are combined with the stoichiometric ratio of COOH groups to epoxy groups:

Is used in an amount of 2 or more.

When this ratio is 2 (corresponding to n ′ = n), higher molecular weights tend to be higher, which is the carboxyl-terminated polymer of formula (II) or the epoxy-terminated of formula (I) It can lead to a significant increase in the viscosity of the polymer, which can cause problems under some circumstances. For a ratio of less than 2 (<2) (corresponding to n ′ <n), especially for a ratio much smaller than 2 (<< 2), this problem becomes very significant. Therefore, a (> 2) value greater than 2 is preferred as this ratio. Typically, values greater than 4 are particularly preferred, especially (>> 2) values considerably greater than 2 (corresponding to n ′ >> n). In these cases, the reaction mixture contains a significant amount of unconverted HOOC-R ¹ -COOH. However, this does not cause any further problems, as discussed below.

It will also be apparent to those skilled in the art that mixtures of polyepoxide PEP and / or carboxyl terminated butadiene / acrylonitrile copolymer CTBN of the formula HOOC-R ¹ -COOH can be used.

In the second step (“termination”), a carboxyl-terminated polymer of formula (II) and a diglycidyl ether DGE of formula (III) are added in a stoichiometric excess (n ″ ≧ n) of diglycidyl. An epoxy-terminated polymer of the following formula (I) is prepared using ether DGE.

が２以上となるような、互いに対する量で用いる。 For this reaction, the polymer of formula (II) and the diglycidyl ether of formula (III) are combined in a stoichiometric ratio of glycidyl ether groups to COOH groups:

Are used in amounts relative to each other such that is 2 or more.

  If this ratio is 2 (corresponding to n ″ = n), the proportion of higher molecular weight will be larger, which may lead to a significantly higher viscosity of the epoxy-terminated polymer of formula (I) This can cause problems under some circumstances. For ratios smaller than 2 (corresponding to n '<n), especially for ratios much smaller than 2 (<< 2), this problem becomes very large. Therefore, a value greater than 2 (> 2) is preferred as this ratio. Typically, values greater than 4 (> 4), in particular values much larger than 2 (>> 2) (corresponding to n ″ >> n) are very preferred.

If the unconverted carboxyl-terminated butadiene / acrylonitrile copolymer CTBN (HOOC-R ¹ -COOH) from the ^first step is still present in the reaction mixture at the start of this second step, Reacts to give an epoxy-terminated polymer of formula (X), known from the prior art.

  This method can ensure that the maximum number of epoxy-terminated polymers that can be used as impact modifiers are present in the final mixture. More particularly, in contrast to prior art methods, it is possible to prevent application properties from deteriorating, in particular large molecular weight distributions leading to high viscosities.

  Those skilled in the art will appreciate that mixtures of carboxyl-terminated polymers of formula (II) and / or diglycidyl ethers of formula (III) DGE can also be used. In such a mode of preparation, a mixture of epoxy-terminated polymers of formula (I) is generated in situ.

  In both steps, an ester is formed. Such reactions of epoxides or glycidyl ethers are known in the art, and reaction conditions therefor are also known. More particularly, it is carried out at a relatively high temperature, typically at a temperature of 100 ° C., preferably about 140 ° C. and optionally with a catalyst, and preferably under a protective gas. Examples of such catalysts are triphenylphosphine, tertiary amines, quaternary phosphonium salts, or quaternary ammonium salts.

  The carboxyl-terminated polymer of formula (II) thus forms a further aspect of the invention. The group, index definitions, options and preferred embodiments shown in formula (II) correspond to those already detailed above for the epoxy-terminated polymer of formula (I).

が２以上に相当する互いに対する量で、この反応に用いることを特徴とする。この方法は既に本明細書中で上に詳細に説明している。 A further aspect of the present invention is a process for preparing a carboxyl-terminated polymer of formula (II) by reaction of polyepoxide PEP with a carboxyl-terminated butadiene / acrylonitrile copolymer CTBN of formula HOOC-R ¹ -COOH, the process comprising: , Polyepoxide PEP and HOOC-R ¹ -COOH, the stoichiometric ratio of COOH groups to epoxy groups:

Are used in this reaction in amounts relative to each other corresponding to 2 or more. This method has already been described in detail herein above.

が２以上に対応した互いに対する量で、この反応に用いることを特徴とする。

A further aspect of the invention is a process for preparing an epoxy-terminated polymer of formula (I) by reaction of a carboxyl-terminated polymer of formula (II) below with a diglycidyl ether DGE of formula (III) below: The stoichiometric ratio of the glycidyl ether group to the COOH group between the polymer of formula (II) below and the diglycidyl ether of formula (III):

Are used in this reaction in amounts relative to each other corresponding to 2 or more.

  This method has already been described in detail herein above.

It will be apparent to those skilled in the art that the epoxy-terminated polymer of formula (I) can be further reacted. For example, more particularly chain extension with polyphenols, in particular with bisphenols, such as bisphenol A, under some circumstances, for example higher molecular weights represented by the following formulas (XIII) and (XIV) Very useful for obtaining epoxy-terminated or phenol-terminated polymers.

In these formulas, the index f is 0 or 1. R ⁹ is here an H, alkyl or alkenyl group, in particular an allyl group.

  A further aspect is a reaction product formed from a carboxyl-terminated polymer of formula (II) and a diamine, (meth) acrylate functional alcohol, or glycidyl ether functional (meth) acrylate, which are exemplified by the following examples: According to the general reaction scheme, in particular, amine-terminated polymers of the formulas (XI), (XI ′) and (XI ″) or (meth) acrylate-terminated polymers of the formulas (XII) and (XII ′) are produced.

In these formulas, R ⁷ is H or methyl and R ⁸ is a divalent group, in particular an alkylene, cycloalkylene, or (poly) oxyalkylene group. Diamines such as 1- (2-aminoethyl) piperazine (DA1), 2-methylpentamethylenediamine (DA2), or 1,2-diaminocyclohexane (DA3), glycidyl (meth) acrylate (GMA), Hydroxy functional (meth) acrylates (HMA) are each used in stoichiometric excess. That is, k, k ′, k ″, k ′ ″, and k ″ ″ are each greater than n.

  Reaction conditions for the formation of amides and esters are known in the literature, and these reaction products, in particular polymers of the formulas (XI), (XI ′), (XI ″), (XII) and (XII ′) It can be applied to the synthesis of

の調製方法であって、その方法は以下の２つの工程を含む。
ａ）予備鎖延長(pre-extension)工程、すなわち、ポリエポキシドＰＥＰを、化学量論的過剰量の式HOOC-Ｒ^１-COOHのカルボキシル末端ブタジエン／アクリロニトリルコポリマーＣＴＢＮと反応させて、既に上述した式（II）のカルボキシル末端ポリマーを得る反応であって、ポリエポキシドＰＥＰとHOOC-Ｒ^１-COOHとを、エポキシ基に対するＣＯＯＨ基の比：

が２以上となる互いに対する量で用いる方法で反応させる工程。ここで、ポリエポキシドＰＥＰおよび式HOOC-Ｒ^１-COOHのカルボキシル末端ブタジエン／アクリロニトリルコポリマーＣＴＢＮは、既に上述したように選択されるべきである。
ｂ）停止（termination）工程、すなわち、式（II）のカルボキシル末端ポリマーと、ジグリシジルエーテル、ジアミン、(メタ)アクリレート官能性アルコール、またはグリシジルエーテル官能性(メタ)アクリレートとを反応させる工程であって、このジグリシジルエーテル、ジアミン、(メタ)アクリレート官能性アルコール、またはグリシジルエーテル官能性(メタ)アクリレートと、式（II）のカルボキシル末端ポリマーとを、式（II）のカルボキシル末端ポリマーの分子のＣＯＯＨ基１モル当たり１モルのジグリシジルエーテル、ジアミン、(メタ)アクリレート官能性アルコール、またはグリシジルエーテル官能性(メタ)アクリレートに相当する互いに対する量で用いる方法で反応させる工程。 A further aspect of the invention is therefore a polymer having end groups of formula (XV):

The method comprises the following two steps.
a) Pre-extension step, ie the reaction of the polyepoxide PEP with a stoichiometric excess of the carboxyl-terminated butadiene / acrylonitrile copolymer CTBN of the formula HOOC-R ¹ -COOH II) Reaction for obtaining a carboxyl-terminated polymer, wherein the polyepoxide PEP and HOOC-R ¹ -COOH are combined with the ratio of COOH groups to epoxy groups:

The process of making it react by the method used by the quantity with respect to each other used as 2 or more. Here, the polyepoxide PEP and the carboxyl-terminated butadiene / acrylonitrile copolymer CTBN of the formula HOOC-R ¹ -COOH should be selected as already described above.
b) Termination step, ie the step of reacting the carboxyl-terminated polymer of formula (II) with diglycidyl ether, diamine, (meth) acrylate functional alcohol, or glycidyl ether functional (meth) acrylate. The diglycidyl ether, diamine, (meth) acrylate functional alcohol, or glycidyl ether functional (meth) acrylate and the carboxyl-terminated polymer of formula (II) Reacting in a manner that is used in amounts relative to each other corresponding to 1 mole of diglycidyl ether, diamine, (meth) acrylate functional alcohol, or glycidyl ether functional (meth) acrylate per mole of COOH groups.

但し、
Ｑ^１が-ＮＨ_２または式（XVI’’）である場合には、Ｑは-ＮＨ-であり、
Ｑ^１が式（XVI’）である場合には、Ｑは-O-または式（XVII）であり、
Ｑ^１が式（XVI）である場合には、Ｑは式（XVII）であることを条件とする。 In the formula (XV), R ¹⁰ is a divalent group, and Q ¹ is a terminal selected from the group consisting of the following formulas (XVI), (XVI ′), (XVI ″), and NH _2. It is a group.

However,
When Q ¹ is —NH ₂ or formula (XVI ″), Q is —NH—
When Q ¹ is formula (XVI ′), Q is —O— or formula (XVII);
If Q ¹ is formula (XVI), then Q is conditional on formula (XVII).

  The polymer having a terminal group of formula (XV) is in particular an epoxy-terminated polymer of formula (I), a carboxyl-terminated polymer of formula (II), a formula (XI), (XI ′) or a formula (XI ′) as described above. It is considered to be an amine-terminated polymer of ') and a (meth) acrylate-terminated polymer of formula (XII) or (XII').

  The carboxyl-terminated polymers of formula (II) prepared in this way, and the polymers with end groups of formula (XV) as described, in particular the epoxy-terminated polymers of formula (I), formulas (XI), (XI ′), Alternatively, an amine-terminated polymer of (XI ″) and a (meth) acrylate-terminated polymer of formula (XII) or (XII ′) can be used as a means to increase the impact resistance of the polymer matrix, so-called impact resistance Useful as an improver.

  A carboxyl-terminated polymer of formula (II) and a polymer having a terminal group of formula (XV), in particular an epoxy-terminated polymer of formula (I), an amine terminus of formula (XI), (XI ′) or (XI ″) The polymer and the (meth) acrylate-terminated polymer of formula (XII) or (XII ′) are preferably liquid or viscous to highly viscous at room temperature. These are preferably processable by conventional means at a temperature of at least 60 ° C. Most preferably, they can be poured at least at 60 ° C. or have a honey-like consistency. If they are highly viscous or solid, they may optionally be dissolved, emulsified or dispersed in a solvent or resin such as a liquid epoxy resin.

  These polymers of formula (I), (II), (XI), (XI ′), (XI ″), (XII), and (XII ′) are crosslinkable compositions, in particular these polymers react. In a system that can be incorporated by The problems with the compositions in which these polymers are used are therefore particularly dependent on the polymer matrix. For example, use (meth) acrylate-terminated polymers of formula (XII) or (XII ′), particularly for (meth) acrylate resins or unsaturated polyester resins that crosslink to the polymer matrix by free radical initiated or UV initiated polymerization reactions Is preferred.

  The epoxy-terminated polymer of formula (I) and the carboxyl-terminated polymer of formula (II) and the amine-terminated polymer of formula (XI), (XI ′) or formula (XI ″) are preferably used in the epoxy resin composition. .

  In the case of the epoxy-terminated polymers of formula (I), these are preferably used in the component in which the epoxy resin A is present. Epoxy resin A may be a liquid epoxy resin of formula (IX) or a solid epoxy resin of formula (VIII). In one embodiment, the composition includes a curing agent B for the epoxy resin along with the epoxy resin A, and the curing agent is activated by increasing the temperature. Such a composition is used in particular as a thermosetting epoxy resin adhesive and cures in the process of heating to a temperature higher than the thermal activation of the thermally activatable curing agent B to form a cured composition. To do.

  In the case of the carboxyl-terminated polymers of formula (II), these can likewise be used in the component in which the epoxy resin A is present.

  However, in the case of carboxyl-terminated polymers of formula (II) or amino-terminated polymers of formula (XI), (XI ') or (XI "), these can also be used in the hardener component. Such curing agent components include curing agents for epoxy resins, such as polyamines or polymercaptans. As a result of mixing these two components, they react with each other, especially at room temperature, to form a cured composition.

  Such a composition can be widely used. Examples are adhesives, sealants, coatings, foams, structural foams, paints, infusion resins, or coatings. They can be used, for example, in construction or civil engineering, in the manufacture or repair of industrial or consumer products. They are adhesives, especially car body construction, and windows, indoor appliances, or transportation aspects, such as water or land vehicles, preferably for manufacturing automobiles, buses, trucks, trains or ships It is particularly preferred to use it as an agent or as a sealant for sealing joints, joints or cavities in industrial production or repair.

  Particularly preferably, such a composition is used as a crash-resistant adhesive, in particular for the construction of transport means, preferably in the OEM department of transport means construction.

  In addition, such compositions are preferably used as structural adhesives for construction and civil engineering or as industrial coatings that can be subjected to significant stresses.

[Example]
Raw materials used:

(Preparation of carboxyl-terminated polymer)
[Spread chain extension at BADGE ] (“CTBN- BADGE- CTBN”)
300.0 g (171 meq COOH) of carboxyl-terminated acrylonitrile / butadiene copolymer (Hycar® CTBN 1300X13), 7.9 g DER 331 (42.8 meq epoxy) to stirrer, nitrogen inlet, and vacuum connection Weighed into a flange-connected flask equipped with a section. The mixture was stirred at 180 ° C. under gentle vacuum for 3 hours. A viscous product was obtained, and the acid value was about 243.4 mg / g KOH (about 416 meq / kg). The product thus obtained was named CTBN1.

[Spread chain extension at HDDGE] ("CTBN- HDDGE- CTBN")
300.0 g (171 meq COOH) of carboxyl-terminated acrylonitrile / butadiene copolymer (Hycar® CTBN 1300X13), 4.42 g of Eurepox RV-H (28.5 meq of epoxy) to stirrer, nitrogen inlet, and vacuum Weighed into a flange-connected flask equipped with a connecting part. The mixture was stirred at 180 ° C. under gentle vacuum for 4 hours. A viscous product was obtained, and the acid value was about 26.3 mg / g KOH (about 468 meq / kg). The product thus obtained was named CTBN2.

(Preparation of epoxy-terminated polymer)
[Termination with BFDGE] ("BFDGE-CTBN- BADGE- CTBN-BFDGE")
100 g (about 41.6 meq COOH) CTBN1 and 150.0 g (822 meq epoxy) Epilox F 17-00 in a flanged flask equipped with stirrer, nitrogen inlet and vacuum connection Weighed out. The mixture was stirred at 180 ° C. for 3 hours under gentle vacuum until a viscous epoxy resin having an epoxy content of about 3.35 eq / kg was obtained. The product thus obtained was named ETBN1.

[Termination with BADGE] (“BADGE-CTBN- HDA- CTBN-BADGE”)
100 g (approximately 46.8 meq COOH) of CTBN2 and 150.0 g (810 meq of EP) of DER 331 were weighed into a flanged flask equipped with a stirrer, nitrogen inlet and vacuum connection. . The mixture was stirred for 3 hours at 180 ° C. under gentle vacuum until a viscous epoxy resin with an epoxy content of about 3.05 eq / kg was obtained. The product thus obtained was named ETBN2.

[ETBN1 with rear chain extended using bisphenol A]
("BFDGE-CTBN- BADGE -CTBN-BFDGE- BPA -BFDGE-CTBN- BADGE -CTBN-BFDGE")
Weigh 150 g (about 504 meq epoxy) ETBN1 and 7.5 g (about 66 meq OH) bisphenol A into a flanged flask equipped with stirrer, nitrogen inlet and vacuum connection. It was. The mixture was stirred at 180 ° C. for 3 hours under gentle vacuum until a viscous epoxy resin with an epoxy content of about 2.77 eq / kg was obtained. The product thus obtained was named ETBN3.

[Badge-terminated CTBN (comparison)] ("BADGE-CTBN-BADGE")
100 g (approx. 57 meq COOH) of carboxyl-terminated acrylonitrile / butadiene copolymer (Hycar® CTBN 1300X13) and 150.0 g (810 meq EP) of DER 331 to stirrer, nitrogen inlet, and vacuum Weighed into a flange connected flask equipped with a connection. The mixture was stirred at 180 ° C. for 3 hours under mild vacuum until a viscous epoxy resin having an epoxy content of about 2.99 eq / kg was obtained. The product thus obtained was named comparative ETBN.

[Effect as an impact resistance improver]
Epoxy-terminated polymers ETBN1, ETBN2, and ETBN3 showed a significant improvement in impact resistance in thermosetting epoxy resin adhesives compared to the comparative polymer (Comparative ETBN).

(Composition example)
According to Table 1, adhesive compositions Z1, Z2, Z3 and a comparative composition (Z comparison 1) were prepared as follows.
First add all ingredients except dicyandiamide to the planetary mixer and stir at 90-100 ° C. under vacuum for 1 hour, then add dicyandiamide and after another 10 minutes of stirring, transfer the mixture to the cartridge. did.

[Preparation of PU Prepolymer (PUPrep)]
150 g Poly-THF 2000 (BASF, OH number 57 mg / g KOH) and 150 g Liquiflex H (Krahn, hydroxyl-terminated polybutadiene, OH number 46 mg / g KOH) at 105 ° C under reduced pressure Dry for 30 minutes. Once the temperature was lowered to 90 ° C., 61.5 g isophorone diisocyanate and 0.14 g dibutyltin dilaurate were added. The reaction was carried out at 90 ° C. under reduced pressure until the NCO content remained constant at 3.10% after 2 hours (calculated NCO content: 3.15%). Next, 96.1 g of cardanol (Cardolite NC-700, Cardolite) was added as a blocking agent. The mixture was further stirred at 105 ° C. under reduced pressure until the NCO content was less than 0.1% after 3.5 hours. The product was then used as PUPrep.

[Test method]
[Tensile strength (TS) (DIN EN ISO 527)]
A sample of the composition was pressed between two Teflon papers to a layer thickness of 2 mm. The composition was then cured at 180 ° C. for 30 minutes. The Teflon (registered trademark) paper was removed and the specimen was punched out in accordance with the DIN standard in a hot state. After one day of storage, the specimen was analyzed at a tensile rate of 2 mm / min under standard climatic conditions.
Tensile strength (“TS”) was measured according to DIN EN ISO 527.

[Mechanical resistance to fracture (ISO 11343)]
Specimens were made from the composition described above and electrogalvanized DC04 steel (eloZn) with dimensions of 90 × 20 × 0.8 mm. The adhesive area was 20 × 30 mm with a layer thickness of 0.3 mm. Curing was performed at 180 ° C. for 30 minutes. The mechanical resistance to break was measured in each case at room temperature and minus 30 ° C. The impact speed was 2 m / s. Fracture energy (FE) (expressed in joules) is the area under the measurement curve (25% -90%, according to ISO 11343).

Claims (18)

Epoxy-terminated polymers of the following formula (I):

Wherein R ¹ is a divalent group after removal of the terminal carboxyl group from the carboxyl-terminated butadiene / acrylonitrile copolymer CTBN;
R ² is the residue after removing n epoxy groups from the polyepoxide PEP;
R ^{2 ′} is H or a group linked to R ² ;
R ³ is a group after removing two glycidyl ether groups from diglycidyl ether DGE;
Y ¹ and Y ² are each independently H or methyl;
n is a 2 a 4),
Epoxy-terminated polymer, characterized in that the polyepoxide PEP is an aliphatic or cycloaliphatic diglycidyl ether. The polyepoxide PEP is a diglycidyl ether of the formula (V ″) or (V ″ ′):

(Wherein r ′ is 1 to 9,
d ′ represents a structural element derived from ethylene oxide, and e ′ represents a structural element derived from propylene oxide;
q ′ is 0 to 10, t ′ is 0 to 10, provided that the sum of q ′ and t ′ is 1 or more)
The epoxy-terminated polymer according to claim 1, wherein R ¹ is represented by the following formula (IV):

(In the formula, a broken line represents a binding site of two carboxyl groups;
b and c represent structural elements derived from butadiene, and a represents a structural element derived from acrylonitrile;
R is a linear or branched alkylene group having 1 to 6 carbon atoms, which may be optionally substituted with an unsaturated group;
q is 40-100;
x is 0.05 to 0.3, m is 0.5 to 0.8, p is 0.1 to 0.2, provided that x + m + p = 1)
The epoxy-terminated polymer according to claim 1, characterized by comprising: The epoxy-terminated polymer according to any one of claims 1 to 3, wherein the polyepoxide PEP is ethylene glycol diglycidyl ether, butanediol diglycidyl ether, or hexanediol diglycidyl ether. R ³ is the following formula (VI) or (VI ′):

Wherein R ′, R ″, and R ″ ′ are each independently H, methyl, or ethyl, z is 0 or 1, and s is 0 or 0.1-12. )
The epoxy-terminated polymer according to any one of claims 1 to 4, characterized by comprising:   The epoxy-terminated polymer according to any one of claims 1 to 4, characterized in that the diglycidyl ether DGE is bisphenol F diglycidyl ether.   The epoxy-terminated polymer according to any one of claims 1 to 4, characterized in that the diglycidyl ether DGE is an aliphatic or alicyclic diglycidyl ether. Diglycidyl ether DGE is a diglycidyl ether of the formula (VI ″) or (VI ″ ′):

(Wherein r is 1 to 9,
d is a structural element derived from ethylene oxide, e is a structural element derived from propylene oxide,
q is 0 to 10, and t is 0 to 10, provided that the sum of q and t is 1 or more. )
The epoxy-terminated polymer according to claim 7, characterized in that   The epoxy-terminated polymer according to claim 7, characterized in that the diglycidyl ether DGE is ethylene glycol diglycidyl ether, butanediol diglycidyl ether, or hexanediol diglycidyl ether. Carboxyl-terminated polymers of the following formula (II):

Wherein R ¹ is a divalent group after removal of the terminal carboxyl group from the carboxyl-terminated butadiene / acrylonitrile copolymer CTBN;
R ² is the residue after removing n epoxy groups from the polyepoxide PEP;
R ^2'is a group linked H or ^{R 2,;}
Y ² is H or methyl;
n is 2-4). R ¹ is represented by the following formula (IV):

(In the formula, a broken line represents a binding site of two carboxyl groups;
b and c represent structural elements derived from butadiene, and a represents a structural element derived from acrylonitrile;
R is a linear or branched alkylene group having 1 to 6 carbon atoms, which may be optionally substituted with an unsaturated group;
q is 40-100;
x is 0.05 to 0.3, m is 0.5 to 0.8, p is 0.1 to 0.2, provided that x + m + p = 1)
The carboxyl-terminated polymer according to claim 10, wherein A process for preparing a carboxyl-terminated polymer according to claim 10 or 11 by reaction of a polyepoxide PEP with a carboxyl-terminated butadiene / acrylonitrile copolymer CTBN of the formula HOOC-R ¹ -COOH, comprising polyepoxide PEP and HOOC-R ¹ -COOH is the stoichiometric ratio of COOH groups to epoxy groups:

Used in this reaction in amounts relative to one another of 2 or more. The epoxy-terminated polymer according to any one of claims 1 to 9 is reacted with a carboxyl-terminated polymer of the following formula (II) according to claim 10 or 11 and a diglycidyl ether of the following formula (III). A process for preparing a polymer of formula (II) and a diglycidyl ether of formula (III) with a stoichiometric ratio of glycidyl ether groups to COOH groups:

Used in this reaction in amounts relative to each other such that is 2 or more.

A composition comprising an epoxy-terminated polymer of formula (I) according to any one of claims 1 to 9, or a carboxyl-terminated polymer of formula (II) according to claim 10 or 11. The composition according to claim 14, further comprising at least one epoxy resin A. The composition according to claim 15, further comprising a curing agent B for epoxy resin activated by an increase in temperature. A cured composition obtained by the addition of the composition of claim 15 and a curing agent for epoxy resins. A cured composition obtained by heating the composition according to claim 16 to a temperature higher than the heat activation temperature of the heat-activatable curing agent B.